US8092778B2 - Method for producing a hydrogen enriched fuel and carbon nanotubes using microwave assisted methane decomposition on catalyst - Google Patents

Method for producing a hydrogen enriched fuel and carbon nanotubes using microwave assisted methane decomposition on catalyst Download PDF

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US8092778B2
US8092778B2 US12/040,883 US4088308A US8092778B2 US 8092778 B2 US8092778 B2 US 8092778B2 US 4088308 A US4088308 A US 4088308A US 8092778 B2 US8092778 B2 US 8092778B2
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flow
catalyst
gas
microwave
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US20080210908A1 (en
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Zhonghua John Zhu
Jiuling Chen
Gaoqing Max Lu
Gregory Solomon
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HYTHANE Co LLC
Uniquest Pty Ltd
Eden Energy Ltd
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Priority to PCT/US2009/034202 priority patent/WO2009145936A2/fr
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/22—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/06—Multi-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0855—Methods of heating the process for making hydrogen or synthesis gas by electromagnetic heating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane

Definitions

  • This invention relates generally to the production of hydrogen fuels, and particularly to a method for producing a hydrogen enriched fuel suitable for use as an alternative fuel along with carbon nanotubes.
  • Gaseous alternative fuels such as hydrogen and natural gas
  • Various processes have been developed for producing hydrogen. These processes include electrolysis, exotic water splitting, and separation from industrial waste streams.
  • Hydrogen can also be produced by reforming natural gas.
  • a multi-step process is used to convert a hydrocarbon fuel, such as methane, propane or natural gas, into a high purity hydrogen gas stream.
  • the steps of the process typically include (1) synthesis gas generation, (2) water-gas shift reaction, and (3) gas purification (e.g., CO and CO 2 removal).
  • the hydrogen gas stream can then be used for a variety of purposes including mixture with other gases to produce an alternative fuel.
  • HYTHANE a particularly clean burning gaseous alternative fuel known as HYTHANE comprises a mixture of hydrogen and natural gas.
  • the prefix “Hy” in HYTHANE is taken from hydrogen.
  • the suffix “thane” in HYTHANE is taken from methane, which is the primary constituent of natural gas.
  • HYTHANE is a registered trademark of Eden Innovations LLC.
  • HYTHANE typically contains about 5% to 7% hydrogen by energy, which corresponds to 15% to 20% hydrogen by volume.
  • steam reformer For producing hydrogen, one type of reformer called a “steam reformer” uses a hydrocarbon fuel and steam (H 2 O). In the steam reformer, the hydrocarbon fuel is reacted in a heated reaction tube containing steam (H 2 O) and one or more catalysts. In general, the production of a high purity hydrogen gas by reforming requires high temperatures (800-900° C.). Steam reforming also produces impurities, particularly CO and CO 2 , which if not removed, are ultimately released to the atmosphere.
  • Another process for producing hydrogen from natural gas involves the thermal decomposition of methane.
  • methane decomposes into hydrogen by the reaction: CH 4 ⁇ C+2H 2
  • thermal decomposition of natural gas has been used in the “Thermal Black Process” for producing carbon black and hydrogen.
  • the energy requirements per mole of hydrogen produced (37.8 kJ/mol H 2 ) is considerably less than the energy requirements of the steam reforming process (63.3 kJ/mol H 2 ).
  • the process still requires high temperatures (e.g., 1400° C.), high equipment costs, and high energy expenditures.
  • a hydrogen production system it would be advantageous for a hydrogen production system to be capable of performance at lower energy expenditures, with a variety of catalysts active for long periods, and with minimal carbon emissions (e.g., CO, CO 2 ).
  • a hydrogen production system it would be advantageous for a hydrogen production system to have a size and configuration adaptable to the production of alternative fuels containing hydrogen.
  • the present disclosure is directed to a method and a system for producing a hydrogen enriched fuel that overcomes many of the shortcomings of prior art hydrogen production systems.
  • a method for producing a hydrogen enriched fuel includes the steps of providing a flow of methane gas, providing a catalyst, selectively heating the catalyst instead of the reactor walls and the methane gas using microwave irradiation at a selected microwave power, directing the flow of methane gas over the catalyst, and controlling the microwave power to produce a product gas having a selected composition.
  • the method can be performed in a reactor having a reaction chamber with microwave transparent walls.
  • the catalyst can comprise a metal, such as a Ni-based compound prepared by coprecipitation.
  • methane (CH 4 ) dissociates into hydrogen (H 2 ) and solid carbon (C) in the form of fibrous carbon.
  • methane slip some of the methane gas fails to react (methane slip) such that the product gas comprises methane and hydrogen.
  • the catalyst is selected and formulated to remain stable under operating conditions (e.g., gas flow rate, microwave power, catalyst amount), such that costs are minimized.
  • the catalyst maintains active characteristics through many hours of reactions.
  • the flow of methane gas and the microwave power can be controlled such that the composition of the product gas approximates the chemical composition of HYTHANE.
  • the product gas can comprise from about 20% to 30% hydrogen by volume, and from about 70% to 80% methane by volume.
  • the product gas contains almost no carbon impurities (e.g., CO, CO 2 ), as carbon is converted to solid fibrous carbon which drops out of the product gas as a useful by-product.
  • the product gas contains only negligible amounts of higher order hydrocarbons (e.g., C 2 H 4 , C 2 H 2 , C 3 H 6 , C 3 H 8 , C 3 H 4 ).
  • a system for producing a hydrogen enriched fuel includes a methane gas source configured to provide a methane gas flow.
  • the system also includes a reactor having a reaction chamber in flow communication with the methane gas source configured to contain a catalyst, and to circulate the methane gas in contact with the catalyst.
  • the system also includes a microwave power source configured to heat the catalyst in the reaction chamber to form a product gas having a selected volumetric percentage of hydrogen and methane.
  • the product gas is further processed to recover hydrogen in substantially pure form.
  • the product gas can be flowed under a vacuum through a Pd/Ag membrane coated on a porous metal or ceramic plate.
  • both a hydrogen enriched fuel and carbon nanotubes are produced.
  • the catalyst comprises a mixture of an Fe-based compound and carbon, which is pretreated in the reactor by microwave irradiation in the presence of CH 4 or H 2 for one to several minutes.
  • MWCNs multi walled carbon nanotubes
  • SWCNs single walled carbon nanotubes
  • FIG. 1 is a flow diagram illustrating steps in a method for producing a hydrogen enriched fuel
  • FIG. 2 is a schematic drawing of a system for producing a hydrogen enriched fuel
  • FIG. 3 is an overlaid graph illustrating CH 4 conversion, H 2 content, and carbon formation versus reaction time for Example 1 using a Ni54Cu27Al catalyst;
  • FIG. 4 is an overlaid graph illustrating CH 4 conversion, H 2 content, and carbon formation versus reaction time for Example 2 using a Ni81Al catalyst;
  • FIG. 5 is an overlaid graph illustrating carbon formation, H 2 content and CH 4 conversion for an alternate embodiment method of Example 3 in which both a hydrogen enriched fuel and carbon nanotubes are produced;
  • FIG. 6 is a transmission electron microscopic image illustrating carbon nanotubes produced by the method of Example 3.
  • FIG. 7 is an overlaid graph illustrating carbon formation, H 2 content and CH 4 conversion for an alternate embodiment method of Example 4 in which both a hydrogen enriched fuel and carbon nanotubes are produced;
  • FIG. 8A is a transmission electron microscopic image illustrating carbon nanotubes produced by the method of Example 4.
  • FIG. 8B is a transmission electron microscopic image illustrating a carbon nanotube produced by the method of Example 4.
  • FIG. 9 is an overlaid graph illustrating carbon formation, H 2 content and CH 4 conversion for an alternate embodiment method of Example 5 in which both a hydrogen enriched fuel and carbon nanotubes are produced;
  • FIG. 10A is a transmission electron microscopic image illustrating carbon nanotubes produced by the method of Example 5.
  • FIG. 10B is a transmission electron microscopic image illustrating carbon nanotubes produced by the method of Example 5.
  • HYTHANE means a hydrogen enriched alternative fuel comprised of hydrogen and methane and impurities included in hydrogen and natural gas.
  • Methane slip means unreacted methane which passes through a system without reacting.
  • Microwave irradiation means electromagnetic irradiation in the range of 0.3 to 300 GHz.
  • Carbon nanotubes are allotropes of carbon having a nanostructure where the length to diameter ratio exceeds 1,000,000.
  • the diameter of a carbon nanotube (CNT) is on the order of a few nanometers, while the length is on the order of millimeters.
  • Carbon nanotubes (CNTs) are generally cylindrical in shape and have a fullerene cap.
  • Carbon nanotubes (CNTs) can have a single wall or multiple walls.
  • a single walled nanotube (SWNT) can have a diameter of close to 1 nanometer.
  • a multi walled nanotube (MWNT) includes multiple layers of graphite rolled in on themselves to form a tube shape.
  • SWNTs Single walled nanotubes
  • MWNTs multi walled nanotubes
  • Carbon nanotubes (CNTs) can be used for a variety of applications including nanoscale electronic devices, high strength materials, field emission devices, and gas storage.
  • the first step comprises “providing a flow of methane gas at a selected flow rate”.
  • the methane gas can be in the form of pure methane gas.
  • the methane gas can be in the form of natural gas obtained from a “fossil fuel” deposit. Natural gas is typically about 90+% methane, along with small amounts of ethane, propane, higher hydrocarbons, and “inerts” like carbon dioxide or nitrogen.
  • the methane gas can be supplied from a tank (or a pipeline) at a selected temperature and pressure.
  • the methane gas is provided at about room temperature (20 to 25° C.), and at about atmospheric pressure (1 atmosphere). Further, the methane gas can be provided at the selected flow rate. In the examples to follow, the selected flow rate of the methane gas is about 120 ml/minute (STP).
  • the method includes the step of “providing a catalyst”.
  • the catalyst is provided in the form of particles having a diameter of from 74 ⁇ m to 140 ⁇ m.
  • the catalyst is preferably contained on a holder, which allows the methane gas to flow freely along the surfaces of the catalyst particles.
  • catalysts in the form of metal oxides can be pre-treated using H 2 to reduce the metal oxide to a metal.
  • a preferred metal for the catalyst comprises Ni, or an alloy containing Ni.
  • the metal can comprise NiAl, or Ni doped with Cu, Pd, Fe, Co, or an oxide such as MgO, ZnO, Mo 2 O 3 or SiO 2 .
  • Specific catalysts include Ni81Al, Ni93Al, Ni77Cu16Al, Ni54Cu27Al and Ni83Mg6Al.
  • nickel based catalyst precursors can be prepared by coprecipitation from a mixed aqueous solution of nitrates with sodium carbonate.
  • Table I provides information on catalyst preparation of nickel-based precursors for the above catalysts. These catalysts were prepared by coprecipitation from a mixed aqueous solution of nitrates with sodium carbonate.
  • Catalyst Preparation Catalyst Composition 1 Ni81Al 81 wt. % NiO-19 wt. % Al 2 O 3 2 Ni93Al 93 wt. % NiO-7 wt. % Al 2 O 3 3 Ni77Cu16Al 77 wt. % NiO-16 wt. % CuO-7 wt. % Al 2 O 3 4 Ni54Cu27Al 54 wt. % NiO-27 wt. % CuO-9 wt. % Al 2 O 3 5 Ni83Mg6Al 83 wt. % NiO-6 Wt. % MgO-11 wt. % Al 2 O 3
  • the catalyst can comprise another metal, such as a metal selected from group VIII of the periodic table including Fe, Co, Ru, Pd and Pt.
  • a metal selected from group VIII of the periodic table including Fe, Co, Ru, Pd and Pt.
  • the catalyst is selected and formulated to remain stable under reaction conditions for long periods of time. In the examples to follow there was no indication that the catalyst was going to be deactivated, even after over 16 hours of reaction time.
  • the method includes the step of “heating the catalyst using microwave irradiation at a selected microwave power”.
  • This step can be performed using a conventional microwave generator and microwave circulator configured to irradiate the catalyst with microwave irradiation.
  • microwave energy selectively heats the metal catalyst instead of the reactor wall and the methane gas, thus significantly saving the energy consumption of the catalyst/microwave heating process.
  • the microwave generator was operated at a power of about 250 watts, and the catalyst was heated to a temperature of from about 600 to 700° C.
  • the method can be practiced at a microwave power that is selected to achieve a desired product gas composition.
  • a representative range for the microwave power can be from 150 watts to 300 watts.
  • the microwave generator was operated at a frequency of 2.45 GHz.
  • the reactor and the holder for the catalyst must be made of a microwave transparent material able to withstand high temperatures.
  • One suitable material for the reactor and the holder comprises quartz.
  • the method includes the step of “directing the flow of methane gas over the catalyst”. This step can be performed by placing the catalyst in a microwave transparent reactor having a reaction chamber configured to contain the catalyst, and to direct the flow of methane gas over the catalyst.
  • the method includes the step of “controlling the microwave power at the selected flow rate to produce a product gas having a selected composition”. This step can be performed using a microwave generator having variable power controls.
  • the system 10 includes a reactor 12 , and a microwave generator 14 .
  • the system also includes a methane supply 16 , a hydrogen supply 18 , and an inert gas supply 20 in flow communication with the reactor 12 .
  • the reactor 12 ( FIG. 2 ) can comprise a conventional tube reactor made of a microwave transparent material, such as quartz.
  • the reactor 12 includes a sealed process chamber 22 having an inlet 26 in flow communication with a supply conduit 24 .
  • the supply conduit 24 ( FIG. 2 ) is in flow communication with a methane conduit 28 via a union 30 , which is in flow communication with the methane supply 16 .
  • the methane conduit 28 includes a methane mass flow controller 32 configured to remotely control the flow of methane gas into the reaction chamber 22 , and shut off valves 34 , 36 on either side of the methane mass flow controller 32 .
  • the methane supply 16 is configured to provide pure methane.
  • the system 10 can include, and the method can be practiced, using another methane source, such as natural gas.
  • the supply conduit 24 ( FIG. 2 ) is also in flow communication with a hydrogen conduit 38 via a union 40 , which is in flow communication with the hydrogen gas supply 18 .
  • the hydrogen conduit 38 includes a needle valve 42 configured to manually regulate the flow of hydrogen gas into the reaction chamber 22 , and a rotameter 44 configured to measure the hydrogen flow.
  • the supply conduit 24 ( FIG. 2 ) is also in flow communication with an inert gas conduit 46 , which is in flow communication with the inert gas supply 20 .
  • the inert gas can comprise Ar or another inert gas, such as He or Ne.
  • the inert gas conduit 46 also includes an inert gas mass flow controller 48 configured to remotely control the flow of inert gas into the reaction chamber 22 , and shut off valves 50 , 52 on either side of the inert gas mass flow controller 48 .
  • the inert gas conduit 46 can be used to purge the reaction chamber 22 .
  • the reactor 12 includes a holder 54 configured to hold a catalyst 56 in the reaction chamber 22 .
  • the holder 54 is made of a microwave transparent material.
  • the holder 54 has a cup like configuration with openings that permit gas flow through the holder 54 and around the catalyst 56 .
  • the holder 54 also includes a handle 58 configured to permit removal of the holder 54 and the catalyst 56 from the reaction chamber 22 .
  • the reactor 12 ( FIG. 2 ) also includes an outlet 60 in flow communication with the reaction chamber 22 .
  • the outlet 60 of the reactor 12 is configured to exhaust the product gas formed in the reaction chamber 22 .
  • the outlet 60 is in flow communication with a gas chromatograph 62 configured to analyze the chemical composition of the product gas exiting the reaction chamber 22 .
  • the gas chromatograph 62 is in flow communication with a vent 64 configured to vent product gases, which have been analyzed to the atmosphere.
  • the outlet 60 of the reactor 12 can also be in flow communication with a product gas storage vessel 66 configured to store the product gas for future use.
  • the microwave generator 14 ( FIG. 2 ) of the system 10 is configured to direct microwave radiation through a microwave circulator 68 , and through a three stub tuner 70 , to the catalyst 56 held on the holder 54 in the reaction chamber 22 .
  • the microwave circulator 68 also includes a cooling system 72 .
  • a microwave adjust plug 74 is configured to remotely adjust the reflected power of the microwave generator 14 .
  • the system 10 ( FIG. 2 ) also includes an infrared temperature sensor 76 configured to measure the temperature of the catalyst 56 .
  • FIG. 3 illustrates the results of CH 4 conversion assisted by microwave heating using Ni54Cu27Al as the catalyst 56 ( FIG. 2 ).
  • Example 1 was a continuous process.
  • the reaction time in hours (h) denotes the length of time that the process was performed.
  • FIG. 3 there are three separate graphs.
  • the lower graph plots the conversion rate “X %” of the CH 4 on the y-axis (expressed as a volume percentage) versus the reaction time in hours on the x-axis.
  • the middle graph plots the content “C %” of H 2 on the y-axis (expressed as a volume percentage) versus the reaction time in hours on the x-axis.
  • the upper graph plots the amount of solid carbon (Solid C (g)) on the y-axis (expressed in grams) versus the reaction time in hours on the x-axis.
  • Example 2 was performed using the same conditions as outlined above for Example 1 but with the catalyst comprising Ni81Al rather than Ni54Cu27Al.
  • FIG. 4 illustrates the results of CH 4 conversion assisted by microwave heating using Ni81Al as the catalyst 56 ( FIG. 2 ).
  • Example 2 was a continuous process.
  • the reaction time in hours (h) denotes the length of time that the process was performed.
  • FIG. 4 there are three separate graphs.
  • the lower graph plots the conversion rate “X %” of the CH 4 on the y-axis (expressed as a volume percentage) versus the reaction time in hours on the x-axis.
  • the middle graph plots the content “C %” of H 2 on the y-axis (expressed as a volume percentage) versus the reaction time in hours on the x-axis.
  • the upper graph plots the amount of solid carbon (Solid C (g)) on the y-axis (expressed in grams) versus the reaction time in hours on the x-axis.
  • An alternate embodiment of the method includes the additional step of further processing the product gas to recover hydrogen in substantially pure form.
  • One method for recovering pure hydrogen is to flow the product gas under a vacuum through a Pd/Ag membrane coated on a porous metal or ceramic substrate.
  • U.S. Pat. No. 6,165,438, to Willms et al. which is incorporated herein by reference, discloses an apparatus and method for the recovery of hydrogen from a gas containing hydrocarbons.
  • Another alternate embodiment of the method produces both a hydrogen enriched fuel and carbon nanotubes (CNTs).
  • This method requires the use of a catalyst mixture which includes an Fe based catalyst mixed with carbon.
  • this method requires that the catalyst be pretreated in the reaction chamber 12 ( FIG. 2 ) using microwave irradiation and exposure to CH 4 or H 2 .
  • Examples 3-5 to follow employ this method.
  • Examples 3 and 4 produce multi walled carbon nanotubes (MWNTs).
  • Example 5 produces single walled carbon nanotubes (SWNTs).
  • the method also requires that the feed gas into the reactor 12 ( FIG. 2 ) includes both a methane gas and a pure hydrogen gas.
  • Catalyst samples for Examples 3-5 were prepared by the coprecipitation method. Catalyst samples employed and their composition are shown in Table 2.
  • Catalyst samples and their composition Catalyst samples Composition FeAl 61 wt. % Fe 2 O 3 -39 wt. % Al 2 O 3 Fe3Al 82 wt. % Fe 2 O 3 -18 wt. % Al 2 O 3 Fe2CuAl 56 wt. % Fe 2 O 3 -26 wt. % CuO-18 wt. % Al 2 O 3 Fe2NiAl 55 wt. % Fe 2 O 3 -27 wt. % CuO-18 wt. % Al 2 O 3 1.2 wt % Fe 2 O 3 /MgO 1.2 wt. % Fe 2 O 3 -98.8 wt. % MgO
  • the catalysts in Examples 3-5 were subjected to a pretreatment step performed in the reactor 12 ( FIG. 2 ). Catalyst samples were in an oxide state, and during pretreatment, were mixed with carbon and reduced with CH 4 or H 2 . The catalyst mixture was induced at a higher microwave forward power (300-1000 W), followed by reduction at a lower power (200 to 450 W) in the presence of CH 4 or H 2 . Vacuum is not needed for the pre-treatment, as atmosphere pressure can be employed.
  • FIG. 5 illustrates the results of the method of Example 3 for producing a hydrogen enriched fuel and multi walled carbon nanotubes (MWNTs) from methane decomposition using microwave heating and an Fe 3 Al catalyst.
  • the weight of the catalyst was 600 mg; the weight of the catalyst mixture was 1000 mg; the flow rate of pure CH 4 was 120 ml/minute; the microwave power output was 325-365 W.
  • X CH4 represents the CH 4 conversion
  • C H2 represents the H 2 volume percentage in the outlet gas
  • Solid C represents carbon formation in grams.
  • FIG. 6 illustrates the multi walled carbon nanotubes (MWNTs) produced by the method of Example 3.
  • Example 3 At the beginning of Example 3, the conversion of CH 4 was about 35% and a product gas containing about 52% H 2 could be obtained, then after 2 hours, the conversion of CH 4 decreased to about 8% and the H 2 content of the corresponding product gas was about 15%. The conversion of CH 4 could be maintained at about 8% for about 2 hours and then decreased again.
  • the solid carbon produced in these conditions included multi-walled carbon nanotubes (MWNT) having a diameter between about 10-40 nm.
  • MWNT multi-walled carbon nanotubes
  • FIG. 7 illustrates the results of the method of Example 4 for producing a hydrogen enriched fuel and multi walled carbon nanotubes (MWNTs) from methane decomposition using microwave heating and an Fe2NiAl catalyst.
  • the weight of the catalyst was 600 mg; the weight of the catalyst mixture was 1000 mg; the flow rate of pure CH 4 was 120 ml/minute; the microwave power output was 220-300 W.
  • X CH4 represents the CH 4 conversion
  • C H2 represents the H 2 volume percentage in the outlet gas
  • Solid C represents carbon formation in grams.
  • FIGS. 8A and 8B illustrate the multi walled carbon nanotubes (MWNTs) produced by the method of Example 4.
  • Example 4 At the beginning of Example 4, the conversion of CH 4 was about 33% and a product gas containing about 50% H 2 could be obtained, then after 5 hours, the conversion of CH 4 decreased to about 10% and the H 2 content of the corresponding product gas was about 18%. The conversion of CH 4 could be maintained at about 10% for about 15 hours and then decreased again.
  • the solid carbon produced in these conditions included multi-walled carbon nanotubes (MWNT) having a diameter between about 10-40 nm.
  • MWNT multi-walled carbon nanotubes
  • FIG. 9 illustrates the results of the method of Example 5 for producing a hydrogen enriched fuel and single walled carbon nanotubes (SWNTs) from methane decomposition using microwave heating and a 1.2 wt % Fe 2 O 3 /MgO catalyst.
  • the weight of the catalyst was 600 mg; the weight of the catalyst mixture was 1000 mg; the flow rate of pure CH 4 was 60 ml/minute; the flow rate of pure H 2 was 60 ml/minute; the microwave power output was 430-650 W.
  • X CH4 represents the CH 4 conversion, C H2 represents the H 2 volume percentage formed from CH 4 decomposition in the outlet gas, and Solid C represents carbon formation in grams.
  • FIGS. 9A and 9B illustrate the single walled carbon nanotubes (SWNTs) produced by the method of Example 5.
  • Example 5 At the beginning of Example 5, the conversion of CH 4 was about 2.5% and a product gas containing about 5% H 2 could be obtained, then after 0.5 hours, the conversion of CH 4 decreased to about 0.3% and the H 2 content of the corresponding product gas was about 0.005%.
  • the solid carbon produced in these conditions included single walled carbon nanotubes (SWNTs) having a diameter between about 5-30 nm.

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